Sorption of butane, propane, ethane, methane, and carbon dioxide on asphaltene

Isotherms of sorption of butane, propane, ethane, methane, and carbon dioxide on an asphaltene sample of known elemental composition were measured. The effect of the pressure and temperature on the shape the sorption isotherms for all the adsorption systems studied was examined. The values of the initial heat of sorption were determined and compared to the energies of interaction of the molecules with asphaltene. The results obtained suggest that asphaltene is a swellable amorphous sorbent.     

Electrocatalysis by foreign metal monolayers: Oxidation of formic acid on platinum

It was demonstrated that some foreign metal monolayers formed by underpotential deposition have pronounced catalytic effects on the oxidation of formic acid on platinum. The explanation of these effects was sought within the framewor of existing data on the formic acid oxidation and the underpotential deposition. It was found that the catalytic effect of foreign metal monolayers originates in the decrease of hydrogen adsorption thus preventing the formation of the main poisoning species COH. At the same time these experiments confirm the previously postulated mechanism of formation of the poisoning species involving adsorbed hydrogen.     

Organoinorganic composites based on tetraethoxysilane and nitrogen polybases

Hybrid organoinorganic composites insoluble in water and organic solvents were prepared by the hydrolysis of tetraethoxysilane in the presence of poly-1-vinylpyrazole, poly-1-vinylimidazole, and poly-4-vinylpyridine. The composition of the composites was determined by the nature of the polymeric nitrogen base and hydrolysis conditions. The composites synthesized showed high sorption activity in the extraction of the [PdCl₄]^2?, [PtCl₆]^2?, and [AuCl₄]^? ions from hydrochloric acid solutions.     

Energy barriers to carousel rearrangements of carbocations: Quantum-chemical calculations vs. experiment

By DFT method energy barriers were calculated for carousel rearrangements of bicyclo[3.1.0]hexenyl, cyclobutenyl, and homotropylium cations. A plausible agreement between calculated and experimental findings was found.     

Phase equilibrium and p s-T-x diagrams of the Ln2S3-LnS2 (Ln = La, Pr, Nd, Sm-Er) systems

A new methodology is proposed and the phase equilibrium is investigated in the Ln₂S₃-LnS₂ systems, in which the low-temperature behavior of nonstoichiometric phases is controlled by the kinetics of the ordering of defects. It is shown that, under equilibrium conditions, the phase equilibrium in the systems is represented not only by a polysulfide with a wide homogeneity region, but also by several (or one) phases of constant irrational compositions combined in the homologous series Ln_nS_2n?1 (n = 3, 4, 7, 8, and 10). The formation of sulfur vacancies and isolated [S₂]^2? ions (which compensate the charge) in the anionic S^2? layer is the basic mechanism of changing the composition of the members of the series. On the basis of structural data, the possible mechanisms of the ordering of defective LnS_2?x polysulfides are examined and it is shown that the formation of stable or metastable phases is a kinetics-controlled process. The role of p _s-T-x diagrams in the interpretations of complex structures of metastable phases from the point of view of attainment of the equilibrium state is discussed.     

Reduction of Alkyl-2-amino-5,6-dialkyl-3-cyanopyridine-4-carboxylates

Reduction of alkyl-2-amino-5,6-dialkyl-3-cyanopyridine-4-carboxylates with sodium borohydride in protic solvents gave rise to 4-amino-3-imino-6,7-dialkyl-1,3-dihydrofuro[3,4-c]pyridines that at hydrolysis in acid medium afforded the corresponding lactones.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 2, 2005, pp. 288–291.Original Russian Text Copyright © 2005 by Vasil’ev, Lyshchikov, Nasakin, Kayukov, Tafeenko.     

Crystal and molecular structures of the complexes of cobalt dichloride with 1-isopropenylimidazole and 1-vinylimidazole

The crystal and molecular structures of bis(1-isopropenylimidazole)dichlorocobalt (C₁₂H₁₆Cl₂·N₄Co) [R 0.036 (R _W 0.089) for 3229 unique reflections with I > 2σ(I)] and tetra(1-vinylimidazole)dichlorocobalt (C₂₀H₂₄Cl₂N₈Co) [R 0.031 (R _W 0.072) for 1863 unique reflections with I > 2σ(I)] were determined. In these molecular complexes, the monodentate terminal 1-alkenylimidazole ligands coordinate to the metal via a “pyridine” nitrogen atom. In C₁₂H₁₆Cl₂N₄Co, the Co atom has a distorted tetrahedral 2N,2Cl coordination. The coordination polyhedron of cobalt in C₂₀H₂₄Cl₂N₈Co is a strongly elongated 4N,2Cl octahedron. The Co-N and Co-Cl bonds [Co-N 2.015(2) and 2.032(4) Å; Co-Cl 2.229(2) Å] in the tetrahedral complex C₁₂H₁₆Cl₂N₄Co are shorter than those in the octahedral complex C₂₀H₂₄Cl₂N₈Co [Co-N 2.134(2) and 2.157(2) Å; Co-Cl 2.518(1) Å]. In the structures of both complexes there are short contacts involving the Cl atoms.     

Effect of the nature of the metal oxide on selective transformation of methane under unsteady conditions in the absence of oxidant in the gaseous phase

The catalytic transformation of methane into higher hydrocarbons was studied under unsteady conditions on oxides of various metals (Pb, Fe, Nb, Ti, Cd, Mo, Mg, Zn, Zr, Bi, Mn), and also on Sr-, La-, Y-, and Mn-containing oxides of perovskite structure. It is shown that the effectiveness of the catalysts not only depends on their chemical composition, but also is determined to a considerable degree by the specific surface of the oxides. L. V. Pisarzhevskii Institute of Physical Chemistry, Academy of Sciences of Ukraine, 252039 Kiev, Prosp. Nauki, 31, Ukraine. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 33, No. 2, pp. 91–95, March–April, 1997.     

Flow injection analysis : Part VI. The determination of phosphate and chloride in blood serum by dialysis and sample dilution

The rapid determination of chloride and inorganic phosphate in blood serum based on continuous flow spectrophotometry was adapted to Flow Injection Analysis by applying dialysis as well as differential dilution of the injected samples. In addition to the manual injection procedure, an automated microsampling unit was developed and used. By continuous dialysis, chloride could be determined reproducibly at a sampling rate of 125 samples per hour at sample volumes of 60 μl or less. A similar sampling rate and high precision were obtained for the determination of inorganic phosphate by using differential dilution.